Tri-n-octylamine-intercalated α-zirconium phosphate (TOA-ZrP) was prepared in the presence of (C4H9)4NOH for the first time. The interlayer distance of (C4H9)4NOH-intercalatedα-zirconium phosphate (B-ZrP) is 14.7 Å, larger than that ofα-ZrP (7.6 Å). The TOA-ZrP sample is highly crystallized with the interlayer distance of 22.3 Å. The molar ratio of TOA toα-ZrP in the intercalation composite was found to be 1/1.21. The composite can find application in solid extraction.